Acrylonitrile-(co)-polymers with reduced surface resistance

ABSTRACT

Acrylonitrile-(co)-polymers with reduced surface resistance which comprise from 1 to 20 % by weight of antistatic agents which are produced by reaction of a polyether diol or an oxalkyl product with a sulfonato dicarbonic ester.

United States Patent [191 Radlmann et al.

[ 1] 3,852,254 1 Dec.3,1974

[ ACRYLONITRILE-(CO)-POLYMERS WITH REDUCED SURFACE RESISTANCE Inventors: Eduard Radlmann; Gunther Nischk,

both of Dormagen, Germany [73] Assignee: Bayer Aktiengesellschaft,

Leverkusen, Germany Filed: May 18, 1973 Appl. No.: 361,528

[30] Foreign Application Priority Data June 10, 1972 Germany 2228362 [52] US. Cl 260/85.5 R, 260/32.6 N, 260/45.85 H, 260/45.85 S, 260/88.7 D,

260/DIG. 16,260/D1G. 19

[51] Int. Cl U C08f 3/76, C08f 15/22, C08f 45/54 [58] Field of Search..... 260/88.7 R, 88.7 D, 85.5 R, 260/85.5 D, 45.85 H, 45.85 S, DIG. 16, DIG.

Primary ExaminerHarry Wong, Jr. Attorney, Agent, or FirmPlumley & Tyner 57] ABSTRACT Acrylonitrile-(co)-polymers with reduced surface resistance which comprise from 1 to 20 by weight of antistatic agents which are produced by reaction of a polyether diol or an oxalkyl product with a sulfonato dicarbonic ester.

6 Claims, N0 Drawings This invention relates to acrylonitrile-(co)-polymers having reduced surface resistance which contain esters of polyalkylene ethers together with dicarboxylic acids which carry sulfonate groups.

Due to their electric surface resistance, shaped products of acrylonitrile-( co)-polymers readily take up an electric charge and are therefore limited in their technical applications.

There have been numerous attempts in the past to reduce the surface resistance to values below Ohm either by applying antistatically active substrates to the surface of the shaped products or by copolymcrising acrylonitrile with suitable comonomers or by introducing antistatically active substances into the melt or solution of the polymers before they are shaped. The simplest of these three methods, which involves the least technical problems, has up to now been that of adding an antistatic agent to the melt or solution before it is processed. This method requires good compatibility of the antistatic agent with the polymer, stability against temperature stresses and resistance to evaporation, hydrolytic influences or removal by washing with water or organic solvents.

The antistatic additives hitherto known are dithiocarbonates, phosphoric acid amides, aminocarboxylic acid amides, ureas, polyalkyleneoxides or polyalkylene oxides which contain terminal sulfonate groups. It was found that the antistatic action was particularly reinforced by the presence of these sulfonate end groups but to obtain a permanent reduction in the electric surface resistance it was necessary to introduce the sulfonate end groups by way of ether groups having resistance to saponification, for example by means of sultones.

We have now found that polyalkylene oxide derivatives in which the sulfonate groups are attached via ester groups in the molecule and not at the end of the chain also have a permanent antistatic action when added to acrylonitrile polymers. These new antistatic additives are in some cases also effective in other synthetic polymers.

This invention thereforeprovides a composition of matter comprising (A) an acrylonitrile polymer selected from the group consisting of a homopolymer and a copolymer and (B) an antistatic agent 1 percent by weight, based on the total composition, of a compound of the general formula n is an integer of from I to 100; m is an integer of from I to I50; R represents hydrogen or the methyl group,

A represents hydrogen, or a radical of the formula in which R represents a linear or branched chain aliphatic group having 1 to 30 carbon atoms, an aryl, alkylaryl or arylalkyl group;

Y represents a single bond or a radical of the formula ene group having I to 20 carbon atoms, an arylene group or a radical of the formula in which R is a single bond, a straight chain or branched chain alkylene group having I to 20 carbo atoms or an arylene group,

B represents the radical O-R or in which R, R,, A and n have the meanings indicated above and Z represents a radical of the formula in which M is an alkali or alkaline earth metal.

Said composition of matter according to the invention is obtained, preferably in the form of threads by a process which comprises addition of an antistatically active compound of the general formula,

in which A, Y,R,Z,B, m and n are as just defined, to spinnable solutions or solvent-free melts of acrylonitrile polymers or -copolymers in amounts from I to 20 percent by weight, based on the total solids content, and then processing the solutions or solvent-free melts into shaped articles.

The antistatic agents added according to the invention can be prepared by condensing a mixture of a sulfonato-benzal or benzyl malonic acid ester of the general formula in which B and Z are asjust defined, by a process which comprises an ester interchange with a polyetherdiol of ethylene oxide and/or propylene oxide or an alkoxylation product of an alcohol, diol, primary or secondary amine or a monoor dicarboxylic acid of the general formula,

sulfonato benzal or benzyl malonic acid esters.

a. 1,456 parts by weight of sodium-2-sulfonatobenzaldehyde, 1,232 parts by weight of diethyl malonate and 17.5 parts by weight of piperidine as catalyst excess atmospheres for l.5-hours at 95C after the addition of parts by weight of Rancy Nickel. After removal of the catalyst by filtration, the dimethylformamide and excess diethyl malonate are distilled off quantitatively under vacuum. Sodium-Z-sulfonatebenzyl-malonic acid diethyl ester remains behind in the form of a liquid which solidifies when cooled to 0C and is solid at room temperature.

Yield: 2341 parts by weight 95.5% of the theory).

b. 192.0 parts by weight of lithium-4-sulfonatobenzaldehyde together with 176.0 parts by weight of diethyl malonate and 7.0 parts by weight of piperidine in a solvent mixture of 500 parts by volume of dimethyl sulfoxide and 300 parts by volume of benzene are heated to the reflux temperature of benzene. The water of condensation forined'is removed azeotropically from the mixture. Condensation is terminated after about 7 hours. The solvent mixture is then removed quantitatively by vacuum distillation. The residue is then dissolved in 600 parts by volume of N,N-dimethylformamide and treated with 20 parts by weight of Rancy nickel at 5O"C for 3 hours to remove traces ofdimethyl sulfoxide. The substance is then filtered and hydrogenated at a hydrogen pressure of 100 excess atmospheres for 2 hours at C after the addition of 20 parts by weight of fresh Raney nickel. Lithium-4- sulfonato-benzyl-malonic acid diethyl ester remains behind after removal of the Raney nickel by filtration and removal of the dimethylformamide and excess diethyl malonate by distillation. The ester is solid but not crystalline at room temperature.

Yield: 326.6 parts by weight 97.2?! of the theory) The following are examples of antistatic additives which can be used in accordance with the invention:

nCo

tives are added to a 27% dimethylformamide solution of apolyacrylonitrile copolymer consisting of 94 parts by weight of acrylonitrile, parts by weight of methylacrylate and 1 part by weight of the sodium salt of methallysulfonic acid having a K-valve of 88 (according to Fikentscher).

The resulting solutions are spun into threads by the dry spinning process in known manner. The surface resistance of the stretched threads is determined after air conditioning at 23C and 50% relative humidity. The.

The results are summarized in Table. l below. A sample of thread without antistatic additive is used for comparison.

r r r 1 o-c1-ncn2 o- CHg -O(CH CH -O -CCII-C our SO3Na -The antistatic agents according to the invention are Table l compatible with acrylonitrile-(co)-polymers and do not separate from mixtures with these polymers. Other ad- Antistatic Surface resistance at 23C and 50% relative ditives such as stabilizers, fillers, dyes, pigments, antiaddi'we after Stmchin g f' g arm w oxidants and the like may also be added without thereg washings washings duction in surface resistance being thereby affected 10'" 10" 10 and without the components separating from the mix- QT WA 7 m m g ture. Such mixtures can easily be processed into 8% by MB 5. 10'" 6.10" 3.10 10% by wt.C 3. 10' 3. 10'" Y 5. 10'" thr 5% by WLD 9. 10:: s. 10:: 9 10::

The acrylonitrile polymers to which this invention 6% by WLE I0 m I m applies can be either pure polyacrylonitrile or acrylonitrile polymers which contain at least 60 percent by The antistatic additives A E can be produced as folweight of polymerised acrylonitrile and up to 40 per- IOW I cent by weight of other copolymerisable compounds A miXture Of 3751) P rt by e ght of a ethoxylfrom the group of vinyl compounds and (meth) -acrylic flied n ny Phenol (m 7 0 termined by the compounds in a copolymerised form. The following are Oil-number), Parts y Weight of the diethyI ester examples of suitable copolymgrisabie Compounds; Of sodium-2-sulfonatobenzal-malonic HCld and (Meth)-acrylic acid esters, (methl-acrylic acid amides, Pf y weight bf Zinc acetate is heated to 150C with vinyl chloride, vinylidene chloride and copolymerisable Surfing under a b f of nitrogen A5 35 mos! of compounds which improve the affinity for acid or basic the ethfsmol has dlstllled a l is pp y dyes means of a water et pump and heating is continued for 2 hours at 150C/15 mm Hg. After cooling to room The Solvents Used may be y Solvent-5 Suitable for temperature, an almost colourless, viscous material pblyabrylonitrlleesPeciiluy dlmbthylformamidewhich has the following constitution remains behind;

It is a great advantage that fibres which contain the S A fi lf f g fg itsg i i f g additives according to the invention do not substand isonon 1 h p 2 il tially alter their surface resistance even after repeated y p eno mw e ermlrfe y t e washing with alkaline detergents. Apart from the excel- CPI-number) 1760 parts by welght 9 ester lent antistatic quality, the acrylonitrile-(co)-polymers 40 of Sodium',zsulfon?to'benzyl'{nalomc and according to the invention are distinguished by their by weght of Zmc acetate heated to good affinity fur basic dyes stirring under a stream of nitrogen and heating is con- 1 tmued until no more ethanol distils off. Stirring is then The following examples are to further illustrate the continued for hours at l600C/l5 mm Hg invemion without ifl plete the ester interchange reaction. After cooling to room temperature, a viscous product which is now only very slightly yellow remains behind. EXAMPLE 1 Yield: 610.0 parts by weight 98.7% of the theory). C. A mixture of 244.0 parts by weight of ethoxylated Varying quantities of the following antistatic addi- 5O isononyl Phenol (mw 488 determined y the number), 135.0 parts by weight of octadecanol-(l), 176.0 parts by weight of the diethyl ester of sodium-2- sulfonato-benzyl-malonic acid and 4.0 parts by weight of zinc acetate is heated to C with stirring under a stream of nitrogen. As soon as no more ethanol distils off, a vacuum of 15 mm Hg is applied and the reaction continued at this vacuum for 1 hour to complete the ester interchange. After cooling to room temperature. a colourless, solid product is obtained. a Yield: 499.3 parts by weight 98.1% of the thoery).

D. 591.5 parts by weight of ethoxylated'N-methylstearylamine (mw 1 183 determined by the CH number), 84.0 parts by weight of the diethyl ester of lithium-4-sulfonato-benzyl-malonic acid and 5 parts by weight of calcium acetate are together heated to C with stirring under a stream of nitrogen. When all the ethanol has been split off, the pressure is reduced to 12 mm Hg and the reaction continued at this pressure for 2 hours. After cooling to room temperature, a pale yellow ester interchange product remains. Yield: 631.6 parts by weight (96.8% of the theory).

E. 568.0 parts by weight of ethoxylated hexane-1,6 diol (mw 568 determined by the OH-number), 324.0 parts by weight of the dimethyl ester of sodium-2- sulfonato-benzyl-malonic acid and 8 parts by weight of zinc acetate are heated to 160C under a stream of nitrogen with stirring. When all the methanol has distilled off, ester interchange is completed by continuing the reaction at a pressure of 14 mm Hg for 3 hours. An almost colourless condensation product which is highly viscous at room temperature and partly solidifies when left to stand for some time remains. Yield: 815.6 parts by weight 98.5% of the theory).

EXAMPLE 2 The antistatic additives mentioned in Example 1 were added in varying quantities as described in Example I to a 27% dimethylformamide solution of a polyacrylonitrile copolymer consisting of 61.3 parts by weight of acrylonitrile, 37 parts by weight of vinylidene chloride and 1.7 parts by weight of the sodium salt of methallylsulfonic acid having a K value of 84 (according to Fikentscher). The threads were dry spun, their surface resistance was determined and the washing processes were carried out as described in Example 1.

The results of measurements of the surface resistance related to the antistatic additive and the number of What we claim is:

l. A composition of matter comprising (A) an acrylonitrile polymer selected from the group consisting of an acrylonitride homopolymer and a copolymer containing at least 60 percent by weight of polymerized acrylonitrile, and (B) 1 20 percent by weight, based on the total composition, of an antistatic agent of the formula n is an integer of from 1l()0;

m is an integer of from l-150;

R is hydrogen or methyl;

A is hydrogen or a radical of the formula R -O,

in which R represents a linear or branched chain aliphatic group containing l30 carbon atoms, aryl. alkylaryl or arylalkyl;

Y is a single bond or a radical of the formula o o 11 ll in which R represents a single bond or a straight chain or branched chain alkylene containing 120 carbon atoms or arylene;

B is O-R,, or

R R losactnlt V in which R, R A and n have the above meanings, and

Z is a radical of the formula ll on 40 -soau 3. The composition of claim 2,. wherein said compound, being copolymerisible is selected from the group consisting of an acrylic acid ester, 21 methacrylic acid ester, an acrylic acid amide, a methacrylic acid amide, vinyl chloride, vinylidene chloride and a mixture thereof.

tistatic finish from acrylonitrile polymers which comprises the addition of an antistatically active compound, as defined in claim 1, to spinnable solutions of acrylonitrile polymers in quantities of l to 20 percent by weight, based on' the total solids content, and spinning the solutions.

UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENTNO. 3,352,254 D E 1 December 3, 1974 INVENT0R(5) I Eduard Radlmann et a1 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 3, formula line 25, "A-X-Y", delete X Column 5 and 6, delete formulas A-D.

Column 7, delete formula top of Columns 7 and 8, insert formulas A-D from Columns 5 and 6.

Signed and Scaled this [SEAL] Sixth Day Of June 1978 A Itest:

R MASON DONALD w. BANNER Attestmg Officer Commissioner of Patents and Trademarks 

1. A COMPOSITION OF MATTER COMPRISING (A) AN ACRYLONITRILE POLYMER SELECTED FROM THE GROUP CONSISTING OF AN ACRYLONITRIDE HOMOPOLYMER AND A COPOLYMER CONTAINING AT LEAST 60 PERCENT BY WEIGHT OF POLYMERIZED ACRYLONITRILE, AND (B) 1-20 PERCENT BY WEIGHT, BASED ON THE TOTAL COMPOSITION, OF AN ANTISTATIC AGENT OF THE FORMULA
 2. The composition of matter of claim 1, wherein said acrylonitrile polymer consists of at least 60 percent by weight of acrylonitrile and up to 40 percent by weight of a compound being copolymerisable with acrylonitrile, selected from the group consisting of a vinyl compound, an acrylic compound, a methacrylic compound and mixtures thereof.
 3. The composition of claim 2, wherein said compound, being copolymerisible is selected from the group consisting of an acrylic acid ester, a methacrylic acid ester, an acrylic acid amide, a methacrylic acid amide, vinyl chloride, vinylidene chloride and a mixture thereof.
 4. The composition of matter of claim 1, containing copolymerised with them, compounds which have acid or basic groups.
 5. Threads and foils of the composition of matter according to claim
 1. 6. A process for the production of threads with an antistatic finish from acrylonitrile polymers which comprises the addition of an antistatically active compound, as defined in claim 1, to spinnable solutions of acrylonitrile polymers in quantities of 1 to 20 percent by weight, based on the total solids content, and spinning the solutions. 